Benzanthrone thiophanthraquinone acridines



Patented Aug. 30, 1949 UNITED STAT ES BENZANTHRQNIEe TH IOPHANTHRAQUINONE KGRIDINES Clarenceliflfielchen,Bridge nn; N. 1-,, and Hemline A. Mero, Wilmington,v Deli, assignorsto E1 1. du Pont de Nemours & Company, Wilmington, DelL, a corporation of Delaware No Drawing. Annlioation-Noucmher. 15, 19:47,. Serial. No. 7853316 4 Claims.

This invention. relates to, the preparation ofnew vat dyes of the alrithraquinone. series, The invention relates more particularly to the preparation oivat, dyes which are alkali. fusion products of. benzanthronyl aminothiophanthraguinone compounds. As in the case of the alkali fusion of the benzanthronyl aminoanthraquinones, where it has never been proved, with absolute certainty that the ring closure takes place only to form the acridine ring, so also in the ring closure of'the compounds of the present invention, while the chemical constitution has not been proved beyond question, these compounds are generally considered as having, and will be represented by; the following structural formula, which is analogous to the formula generally accepted in the alkali fusion of the benzanthronylmminm anthraquinones inwhich AA is a thiopheneringof'the tormula:

These dyes arethereiore considered; to hebenzanthronyl aminothiophanthraq uinone.acridihes comparable to. the benzanthronyleaminoanthraquinone aoridines of literature but which carry in the vattable nucleus a thiophene ring. They dissolve in concentrated sulfuric acid to give green solutiona, and dye cellulose fibers from an alkaline hydrosulfite or sodium sulfide vat in olive green to gray shades of exceptionally good fastness properties.

It is therefore an object. of this invention to produce new vat dyes of the benzanthronylaminothiophanthraquinone acridine type which are outstanding in fastnessproperties and depth of shade.

The dyestuffs of this invention are prepared by alkali-fusion of the benzanthronylaminothiophanthraquinone compounds" by treatment with alkaline condensing" agents, generally using an alcoholic medium. Fusion may be carried out under a wide variety of reaction conditions as to temperature andtime, depending uponthe e the preparation of these new dy s.-

results; although temperatures outside 01' this poured into one liter of cold water.

ange are occasionally necessary. The time of reactiondepends upon the temperature chosen and" the reactants-used:

The benzanthronyl aminothiophanthraquinones, which may be fused with caustic alkalies to produce the acridine derivatives of this invention, are those more particularly disclosed and claimed in our co-pending application Serial No. 786,335, now Batent' 2,480,109; filed concurrently herewith and which have the general formula:

wherein the thiophanthraquinonyl radical is at tached to the a-4 1 in the 5- or S-pcsition and X in each case is hydrogen or halogen. These compounds maybe prepared by condensing one mol of a 5- or 8-aminothiophanthraquinone with a monoor dihalogen benzanthrone (preferably the bromo-benzanthrone) by the condensation methods ordinarily us d n ensing aminoanthraquinone with halogen anthr quin ne.

The following examples are given to illustrate The parts used are by weight, unless otherwise specified.

Example 1 A mixture -of'38: parts of'methanoland parts of potassium hydroxide is stirred at 1.25.-130 C. until smooth, then 19 parts of fiiBz-l-benzanthronylaminol-thiophanthraquinone are added at 1369-" 3; The charge is stirred at 2 C. for one hour, diluted with water and The slurry is stirred several hours at room temperature, filtered and the cake is washed alkali-free with water and dried. The 5-[Bz-l-benzanthronylamino]-thiophanthraquinone acridine may be represented by the formula:

It dissolves in a concentrated sulfuric acid to give a green colored solution, and dyes vegetable fibers from bluish-green alkaline-hydrosulfiteor sodium sulfide vats in greenish-olive shades of outstanding light fastness.

Example 2 in which bromine is largely lost during the fusion and it is not known whether the 6-position enters into any other reaction or not. The product, which is acid pasted by customary methods, gives a green solution in concentrated sulfuric acid, and dyes vegetable fibers gray shades of outstanding light fastness from a green alkalinehydrosulfite vat, or a bluish-green sodium sulfite vat.

In similar fashion, 6,Bz-1-dibromobenzanthrone may be condensed with B-aminothiophanthraquinone and the resulting anthrimide fused under alkaline conditions.

Example 3 the caustic alkali fusions, as illustrated in the above examples, to give dyes of similar dyeing characteristics and fastness properties, such as the condensation products of 2-chloro-5-aminothiophanthraquinone or 2-bromo-5-aminothiophanthraquinone with Bz-l-bromobenzanthrone or Bz-l-chlorobenzanthrone; one mol of S-aminothiophanthraquinone with one mol of 6,Bz-1-dichlorobenzanthrone; 2-chl0r0-5-aminothi0phanthraquinone or 2-bromo-5-aminothiophanthraquinone with 6,Bz-l-dibromobenzanthrone or :6,Bz-l-dichlorobenzanthrone; 2-chloro-8-aminothiophanthraquinone or 2-bromo-8-aminothiophanthraquinone with 6,Bz-1-dibromobenzanthrone, or 6,Bz-1-dichlorobenzanthrone.

During a caustic alkali fusion of the benzanthronylaminothiophanthraquinones which carry halogen in the molecule, particularly in the 2- position of the thiophene ring or the 6-position of the benzanthronc nucleus, such halogen is largely lost and it has been impossible to determine whether or not during the fusion the position in the molecule where the halogen is eliminated also enters into the reaction. The alkali fusion products of the halogen substituted compounds show dyeing properties similar to those which do not contain halogen substituents in the molecule, and exhibit the same good light fastness and depth of shade.

The dyes of this invention all show a very marked improvement in depth of shade and an To 22 parts of methanol are added 43.5 parts i of potassium hydroxide gradually, while heating slowly to l25-130 C. When the melt is smooth, 11 parts of 8-[Bz-l-benzanthronylamino]-thiophanthraquinone are added slowly at 130-135 It dyes vegetable fibers from a greenish alkalinehydrosulfite vat in olive-green shades of outstanding light fastness.

Other halogen-containing benzanthronylaminothiophanthraquinones may be subjected to unexpected increase in light fastness over their anthraquinone analogs, which is especially surprising since the benzanthronylamino-anthraquinone acridines are considered to exhibit outstanding light fastness and a further improve ment would not be expected nor could it be predicted on the basis of other known dyestufis containing sulfur. It has also been found that these new colors are more easily vattable and that they are therefore excellent printing colors which build up to deeper shades than can normally be achieved with analogous anthraquinone colors. Since these colors are readily vattable with sodium sulfide, they can be applied in the same manner as the sulfur colors and are therefore valuable additions in that particular field of vat dyes, giving colors of fastness properties not heretofore available in that class.

We claim:

1, The vat dyes obtained by the caustic alkali condensation of the benzanthronylaminothiophanthraquinones of the formula:

5? E 3 W 8 i wherein the thiophanthraquinonyl radical is attached to the -N in one of the positions 5 and 8, and wherein X in each case stands for an atom of the group consisting of hydrogen and halogen, which condensation products dye cotton from an alkaline hydrosulfite vat in greenish-olive and gray shades.

2. The vat dye obtained by the caustic alkali 5 condensation of the benzanthronylaminothio- 4. The vat dye obtained by the caustic alkali phanthraquinone of the formula: condensation of the benzanthronylaminothiophanthraquinone of the formula:

l H N 5 0 N I 0 7 II \s 10 J 0 O I l which condensation product dyes cotton from an alkaline hydrosulfite vat in greenish-olive shades. which condensation product dyes cotton from an 3. The vat dye obtained by the caustic alkali alkaline hydrosulfite vat in gray shades.

condensation of the benzanthronylaminothio- CLARENCE F. BELCI-IER.

phanthraquinone of the formula: LORRAINE A. MERO.

REFERENCES CITED 1 N The following references are of record in the Q file of this patent:

/ UNITED STATES PATENTS Number Name Date 2,212,029 Lulek Aug. 20, 1940 A O OTHER REFERENCES which condensation product dyes cotton from an Fieser et al., Organic Chemistry (D. C. alkaline hydrosulfite vat in greenish-olive shades. Heath; Boston; 1944) page 527. 

